Preparation of vitamin-fortified meals



' Patented Jan. 11, 1949 PREPARATION OF VITAMIN -FORTIFIE.D MEALS Loran 0. Buxton, Maplewood, N. 1., assignor to N opco Chemical Co New Jersey mpany, a corporation of No Drawing. Application June a, 1946,

Serial No. 674,030

20 Claims. (Cl. 99-11) 1 This invention relates to methods for preparing free-flowing vitamin-containing vegetable meals and to the meals prepared thereby, and is a continuation-in-part of copending application Serial No. 528,355 now Patent No. 2,426,486, filed March 27, 1944, by Buxton and Dryden, and my copending application Serial No. 674,031 filed concurrently herewith.

Fat-soluble vitamin-containing materials as,

oils as sources of vitamins, the product was usually an oily meal of an unpalatable nature. Whenever the added oil was in excess of 5 or 6%.

the meal particles were unctuous in nature and readily tended to cake thereby rendering mixing difficult. In addition, the oil on the exterior surfaces of the meal particles was subject to the destruction of its vitamin content by oxidation.

Various proposals have been made for producing stable vitamin-containing materials of high potency in a dry, granular form but little success has been attained along this line. Some of the suggestions of this nature related to incorporating fish liver oils in molten paraflin or gums and impregnating vegetable matter with the mixture whereby the vitamin-containing oils were inclosed in a film of wax or gum upon cooling. Such products did not prove to be very stable as regards the protection of vitamin material and the use of waxes and gums was undesirable from a physiological standpoint. The waxes and gums not only were not assimilable by animal bodies but also interfered with the assimilation of vitamins contained therein.

In the copending application of Buxton and Konen Serial No. 442,079, filed May 7, 1942, now Patent 2,401,293, a dry carrier with a nonunctuous exterior is prepared by treating vegetable materials with a vitamin-concentrate admixed with crude vegetable oils. While this method has attained considerable success, it is to be noted that it is limited to the preparation of materials having a total fat content not in excess of 30%. Moreover, this process does not provide for the formation or liberation of certain antioxidant 2 substances in vegetable meals in the manne disclosed in Patent 2,426,486.

An object of the present invention is the preparation of free-flowing, vitamin-containing vegetable meals of substantial oleaginous content.

A second objectof the invention is'th'e reduction or elimination of oiliness from the exterior of particles of vitamin-containing vegetable meals of substantial oleaginous vitamin content.

A third object of the invention is the preparation of stabilized, dry, vitamin-containg vegetable meals containing substantial proportions of oleaginous matter.

A fourth object of the invention is the preparation of vitamin-containing vegetable meals of substantial oleaginous content and improved oxidation-resisting properties.

A fifth object of the invention is to provide a method for incorporating vitamin-containing oils into vegetable meals'of high oleaginous content.

Another object of the invention is the preparation of vegetable meals of increased vitamin potency;

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The present invention concerns the treatment of vegetable meals and vitamin-containing oils with ammonia and a solvent miscible with the oils. Thereafter the ammonia and-solvent are separated from the mixture of meal and vitamin oil. This operation is usually accomplished by volatilizing the ammonia and solvent at a moderate temperature as, for example, by air-drying.

In order to increase the vitamin potency of edible vegetable meals, it is highly desirable to be able to add more than 5 or 6% of oils containing fat-soluble vitamins to the meals and still have a free-flowing product. Meals which will flow in this manner are composed of particles which at least appear to have dry, nonunctuous surfaces. However, surfaces having only slight traces of oiliness, while not dry, are substantially nonunctuous and free-flowing. In my copending application Serial No. 674,031 is disclosed a methodof substantially eliminating surface oiliness from oil-bearing vegetable meals having less than 50% content of fatty material. In the present invention, this method is utilized in conjunction with the addition of vitamin-containing oils to vegetable meals to yield an edible meal of enhanced vitamin potency and increased resistance to oxidation. When the total oleaginous content, including the added vitamin oil, of the product exceeds 50% of the total weight, the resulting product cannot be said to be freeflowing and nonunctuous in character, although 3 the surface oiliness and caking tendencies of the material are greatly reduced by the treatment. By this improved process it is possible to obtain from the vegetable matter products of high vitamin content. The treatment is expedited by heating but is operative. at any temperature above the\ congealing point of the liquid mixture. However, the use of temperatures above the boiling point of the solvent or above about 100 C. is undesirable as it causes excessive losses of ammonia and solvent. In addition, a partial decomposition of many vegetable meals occurs at temperatures above 100 C. Good results have been obtained in carrying out the mixing for one hour at 50 to 60 C.

Since the products possess utility in the preparation of foods for poultry, livestock and human beings, the meal should be selected from the cereal grains or other appropriate sources containing no constituents harmful to animal life. and preferably including considerable quantities of materials of nutritive value. Suitable meals include, inter alia, those obtained from cottonseed, maize, fiaxseed, sesame seed, soya beans, peanuts, copra, cocoa beans, wheat germ, corn germ, barley, oats, rye, wheat, alfalfa, rice bran, palm kernels, dried grass, and all types of edible nuts. The fineness to which the meal is ground is a matter of choice as the treatment is operative on any vegetable material not covered by an impermeable coating. Coarse particles will require a somewhat longer mixing with the treating liquid, and a considerable expenditure of power is required in grinding very fine meals. In general, the employment of meals which will pass through any screen in the range from 40-100 mesh is recommended.

The ammonia may be utilized in any form; accordingly, it is to be understood that the term ammonia" is used herein in the generic sense to denote ammonia gas (NHa), liquid ammonia and ammonia dissolved in water or any other suitable solvent. In" employing gaseous or liquid ammonia, suitable pressure vessels or artificially cooled equipment will be required. The preferred and most convenient method of contacting the raw materials with ammonia is in the form of a concentrated ammonium hydroxide solution containing approximately 28% by weight. The quantity of active NH: used in the present process may vary very widely and from a considerable number of experiments it has been found that the attributes of the product of this invention may be realized in at least some degree when 1000 parts by weight of the mixture of vegetable meal and vitamin oil are treated with from 1 to 100 parts by weight of N53, corresponding to 3 to 350 parts of concentrated ammonium hydroxide. However, the preferred proportions are in the range of 5 to 50 parts of NH3, which is equivalent to 18 to 180 parts by weight of concentrated ammonium hydroxide, for 1000 parts of the combination of meal and vitamin oil.

Appropriate solvents comprise organic solvents which are miscible with or dissolve the major portion, and preferably all, of the oils and fatty constituents in the vitamin-containing oil and the meal to be treated. Further, the solvent must be compatible with ammonia; that is, not react with ammonia. The solvent may consist of a single chemical compound or a mixture of several of these. Suitable solvents for the instant method include, inter alia, hexane, heptane, octane, ethylene dichloride, 'trichlorethyiene, carbon tetrachloride, cyclohexane, methyl cyclohexane, benzene, acetone, isopropanol, diacetone alcohol, and the like. It must be realized that the performance of these substance varies considerably. Experiments carried out to date have indicated acetone to be highly superior for the present purposes to the other compounds listed. While it is preferable to select a solvent of substantial volatility at room temperature in order to expedite the air-drying step, this is not essential as the solvent can be vaporized by heating and/or at reduced pressures. It is necessary that the solvent be one which can be evaporated at temperatures below those which cause decomposition of v the vegetable meal.

A solvent mixture may include a substance immiscible with fatty materials, provided that a solvent of the class defined above is also present. In such cases the proportion of such fat-immiscible ingredient must be kept low enough to not appreciably affect the miscibility or solvent power of-the solvent mixture in respect to fatty materials. Examples of the type of ingredient mentioned include the lower alcohols as, for instance, methanol, ethanol, propanol, etc. The action of these alcohols is not understood but their incorporation into a solvent mixture in minor amounts appears to increase the activeness of the treatment of certain vegetable meals. It is to be noted that these alcohols are all highly polar,

and this feature may have some bearing on their effect in the solvent mixture.

The quantity of solvent to be employed depends almost entirely on the quantity of vegetable meal present. For each 100 parts by weight of vegetable meal, a minimum of about 8 parts by weight of the solvent is required. Large excesses of solvent may be added, but this practice merely increases the cost of processing and lengthens the time required for drying. In general, the preferred range is from 20 to 60 parts by weight of solvent for each parts of meal which produces economical mixtures which are usually of readily kneadable consistency. The preferred consistency of the mass is of the character of wet mush, that is, a plastic mass rather I than a slurry capable of being poured.

Any suitable natural or synthetic material rich in any one or more of the fat-soluble vitamins, e. g., A, D, E and K, may be used in producing the products of the invention, the corresponding provitamins being included under the generic expression vitamins. It is preferred to use animal, vegetable or fish oils rich in the fat-soluble vitamins, such as cod liver oil, shark liver oil, halibut oil, sardine oil, tuna oil, tuna liver oil, palm and like oils, concentrates thereof, or such oils fortified with vitamin concentrates. Other sources of the fat-soluble vitamins such as antirachitic activated sterols and the like may also be used either alone or in combination with any of the aforementioned or other vitamin-containing materials. The quantity of the vitamin-containing oil to be added to the vegetable meal is a matter of choice, subject to the rule that a freeflowing product whose particles have a substantially nonunctuous exterior-cannot be obtained where the sum of the original fatty content of the meal and that of the vitamin oil exceeds 50% of the weight of the product.

For a fuller understanding of the nature and objects of the invention, reference should be had to the following examples which are given merely to further-illustrate the invention and are not to be construed in a limiting sense, all parts given being by weight. It will be noted that the properties and characteristics of the products of Examples I to DIN, inclusive, are set forth in Tables 1 and 2 rather than in the examples themselves.

EXAMPLE A EXAMPLE B Aprocessed oil with a vitamin A content ascertained to be 417,000 U. S. P. units per gram by the analytical procedure of Example A.

This oil was produced in accordance with the process of my copending application Serial No. 450,757, filed July 13, 1942, now Patent 2,412,766. Soupfln shark oil was saponifled to 85% of its saponiflcation value, and the unsaponiflable portion was extracted from the saponifled mass by using ethylene dichloridewhich was thereafter distilled off from the unsaponifiable matter. This unsaponifiable matter was treated with methanol at a low temperature, and the methanol fraction containing the vitamin A alcohols was drawn off. The residue was an oil containing the vitamin A esters and constituted the processed oil of this example.

EXAMPLE C A fish liver oil consisting of equalportions by weight of the liver oils of soupfin sharks and dogflsh.- The vitamin A potency was found to be 67,600 U. S. P. units per gram of oil by the same procedure used in Example A.

EXAMPLE I Raw materials Grams Vitamin oil of Example A 120 Wheat germ flour (sieved) 250 Expeller linseed oil meal 630 Treating agents Q None.

-The two meals were placed in a small Read mixer, which is similar to the type of mixer employed forkneading dough. As soon as the mixture was uniform, the oil was added slowly. The mass was then mixed for one hour at room temperature and without the use of a condenser.

Since this was a blank or control sample, for

purposes of comparison-the mass was given no further treatment.

I EXAMPLE II Raw materials Same as in Example I.

Treating agents Grams Concentrated ammonium hydroxide (28% NHa) Acetone. 400

The oil was poured into a -liter flask con-- taining the wheat germ flour and acetone. After thoroughly shaking the mixture, the ammonium hydroxide was added, and the mass slowly refluxed for one hour in an atmosphere of nitrogen. As the -mixing of the solvent and meal proved unsatisfactory, the mass was transferred to a Read mixer. The linseed meal was added and the mixer operated for. one hour at room temperature. Then the mass was air-dried, and the few lumps were broken up with a spatula.

ExAMrLr: III

Raw materials Same as in Example I.

Treating agents Grams Conc. ammonium hydroxide (28%) 22.5 Acetone s. 400

In this, and in all subsequent examples, unless otherwise stated, the Read mixer was equipped with a vapor condenser and heated to approximately 50 C. by passing hot water through the water jacket. The two meals and acetone were mixed to uniformity; then the oil was poured onto the moist meal. After mixing for one or two minutes, the ammonia was added and the mixer operated for one hour. After air-drying, the product was passed through a 10 mesh sieve to breakup lumps.

EXAMPLE IV Raw materials Same as in Example I.

The procedure differed from that of Example III only in regard to the use of a larger amount of ammonia.

EXAMPLE V Raw materials Same as in Example I.

Treating agents Grams Acetone 400 The procedure employed was identical with that of Example 111, except that no ammonia was used in this blank or control experiment.

ExAMrLE VI Raw materials Grams Vitamin oil of Example A 120 Expeller linseed oil meal-- 880 Treating agents None.

This was, a blank sample for comparison with Example VII. The oil was poured slowly into the meal being stirred in the mixer.' Mixing was continued for an hour atroom temperature.

ExAMrLE Raul materials I Same as in Example VI.

Treating agents Grams Cone. ammonium hydroxide (28%) 45 Acetone 400 7 Exmu: V111 Raw materials Grams Vitamin oil of Example A 250 Wheat germ flour (sieved) 250 Expeller linseed oil meal 500 1,000 Treating agents I Grams Conc. ammonium hydroxide (28% N111)---" 90 Acetone 400 After mixing the two meals with the acetone, the resulting mass was wet but not fluid. The addition of the vitamin oil made the mixture 50 fluid that it could be poured. Upon addition of the ammonium hydroxide, the mass immediately lost its fluidity and became granular. Thereafter, the wet meal was kneaded for one hour in the mixer, air-dried, and screened through a 10 mesh sieve to reduce the lumps.

EXAMPLE IX Raw materials The procedure was the same as that of Example VIII.

EXAMPLE XI Treating Agents Grams Cone. ammonium hydroxide (28% NHa) 135 Actone- I 400 The procedure of Example VIII was employed.

EXAMPLE XII Raw materials Grams Vitamin oil of Example C 100 Black soybean meal (finely ground) 900 Treating agents None.

This was a control sample so the only treatment consisted of mixing the oil and meal in a Read mixer for one hour at room temperature.

Examu: m

Raw materials Same as in Example XII.

Treating agents Grams Conc. ammonium hydroxide (28% NHa) 45 Ace 400 The oil, acetone and ammonia were added successively to the meal being kneaded in the mixer. Mixing was continued for one hour at approximately 50 C. then the mass was air-dried.

Exam-1.1: XIV

Raw materials Grams Vitamin oil 01 Example 0 100 Flaxseed meal (finely ground) 900 The original oil content of the flaxseed meal was found to be 40.4% by weight. The vitamin oil was added to the meal with the mixer operating. After 30 minutes of mixing, it was apparent that the meal was absorbing little or none of the vitamin oil. The mass was very oily and formed lumps or balls.

Treating agents Grams Raw mam Cone. ammonium hydroxide (28% NI-Is) 07.5 Grams Aoetrmn 400 Vitamin oil of Example B 3 00 Methanol 80 Wheat germ flour (sieved) 350 A mixture of the treating agents was added to Expeller linseed oil meal 350 the oil-meal mass. After mixing foronehour at about 50 C.,. the treated product was air-dried to 1,000 remove the treating agents.

TABLE 1 il 3 1; 235 A to NH on F E erm can no no 4 a sin Eample Added, Flour, Meal, Meal, Grams Grams Product, 0111119 Grams Grams Grams Percent 120 250 030 0 0 0 blank 17. 5 oily, caked easily. 120 250 630 0 0 400 45. 0 l7. 5 very slightly oily, free'flowing. 120 250 630 0 0 400 22. 5 17. 5 dry, nonoily. V 120 250 630 0 0 400 90. 0 17. 5 very dry, nonoily. 120 250 030 0 0 400 blank 17. 5 same as I, much oilier than III and IV. 120 0 880 0 0 0 blank very oily, caked heavily. 120 0 880 0 0 400 45.0 dry, nonoily. 250 250 500 0 0 400 90.0 30.0 o. 400 300 300 0 0 400 00. 0 44. 7 similar to I, but somewhat free-flowing. 400 0 600 0 0 400 90. 0 44. 5 less oily than I and IX, fairly tree-flowing. 300 350 350 0 0 400 135.0 35. 3 dry, nonoily. 100 0 0 900 0 0 blank 26.0 oily, caked easily. 100 0 0 900 0 400 45. 0 26. 0 dry, nonoily. 100 0 0 0 900 l 480 67. 5 47. 0 slightly oily, free-flowing.

l Mixture of 400 grams acetone and grams methanol.

- .In considering the data in Table 1, it will immediately be noted that surprising quantities of oil, ranging up to about of the total weight, can be incorporated into vegetable meals by the present process.

specific features of the invention herein described and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween; and that they are intended to be inclusive in scope and not exclusive, in that, if

1 Test conducted at 50 0. instead of 30 0.

vention are more stable in respect to maintaining their vitamin potency for substantial periods than the blank or control samples. This is especially evident from the column setting forth the loss of vitamin content after 3 months at 30 C.

It should be noted that the treated meal of Example VII shows a striking improvement over the control sample of Example VI in maintenance of'vitamin potency.

While a sample produced by the procedure of Example VIII shows a larger loss of vitamin content than the product of Example I after aging for 2 months at 30 0., the control sample in this instance is not thought to furnish an adequate comparison in view of its vitamin oil content of less than half that of Example VIII. In general, it is evident that the new products are of greater stability in respect to efiectlve vitamin A content.

Since certain changes in carrying out the above process and certain modifications in the composition which embody the invention may be made without departing from its scope, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense. It is' also to be understood. that the following claims are intended to cover all the generic and All of the ammonia-solvent-treated products 5 desired, other materials may be added to my novel are of free-flowing character whereas the uncomposition of matter herein claimed without treated blank samples of "Examples I, V, VI and departing from. the spirit of the invention. Par- XII of similar or lower fatty content are meals ticularly it is to be understood that in said claims, with unctuous coatings which readily cake. m ingredients or components recited in the singular The present method is not a mere washing of are intended to include compatible mixtures of surface oil from the particles of meal as evidenced said ingredients wherever the sense permits. y the Pr d t 01 Example V which had the same Having described my invention, what I claim characteristics as the control sample of Example I a e nd e ir t secure by tt t t 1 despite the addition of a solvent but no ammonia l6 -1. A process for preparing a free-flowing, oxito the mix. dation-resistant, vitamin-fortified, edible vege- Example XIV is of mterestin showing that the table meal which comprises thoroughly impregammonia-solvent t eatme t in 801118 manner nating an edible vegetable meal by mixing therefects the structure or composition of the vegetable with anoil containing fat-soluble vitamin mamatter. In this ase, 011, which th untreated 20 terial, ammonia and a solvent compatible with fiaxseed meal was incapable of absorbing prior to m i and i i ith b t nti prothe treatment, Was readily bs in the p portion of the oleaglnous matter in the mixture, ence of a mi tu e of o e e a d meth said, vitamin-containing oil being added in such anol into the interior of the meal particlesquantity that the total quantity of oleaginous It was distin y rp i ing to find the treated matter in the combined meal and vitamin-conp du t f -fl w n a d p s ssin only sl ht taining 011 does not exceed 50% of the total surface oiliness. weight of vegetable meal and vitamin-contain- TABLE 2 V L "AL n Product Iier cent Vitamin A lgestroyed F u g, NHOH' 33 PVLHA inPi'oduct at30 c.

Mmpe Added, USP units grams product,

Grams per gram per cent grain- 11110. 1% mo. 2mo. 3mo.

120 41,200 I 120 41,200 45.0 120 4!,200 22.5 120 41,200 00.0 120 41,200 blank 120 41,200 blank 120 41,200 45.0 1 250 41,200 90.0 400 41,200 00.0 .400 I 41.200 00.0 300 417,000 135.0 7 67,600 [blank 100 67,000] 45.0 100 01,000 01.5

ing oil, and removing the ammonia and said solvent from the meal in such manner that substantially all of the oleaginous matter remains with p the meal.

taining oil in the mixture, and at least 8 parts by weight of solvent are used for each 100 parts of untreated vegetable meal.

4. The process of claim 1 in which about 1 to 100 parts by weight of ammonia are used for each 1000 parts of vegetable meal and vitamincontaining oil in the mixture, and the solvent comprises at least 8 parts by weight of acetone for each 100 parts of untreated vegetable meal.

5. The process of claim 1 in which about 1 to 100 parts by weight of ammonia are used for each 1000 parts of vegetablemeal and vitamin-containing oil in the mixture, and the solvent comprises at least 8 parts by weight of a blend of acetone methanol ior each 100 parts of untreated vegetable meal.

6. The process 01 claim 1 in which about 5 to 50 parts by weight of NH: in concentrated aqueous solution are used for each 1000 parts or vegetable meal and vitamin-containing oil in the mixture, and at least 8 parts by weight of said solvent are used tor each 100 parts of untreated vegetable meal.

7. The process of claim 1 in which about 5 to 50 parts by weight NH: in concentrated aqueous solution are used ior each 1000 parts of vegetable meal and vitamin-containing oil in the mixture, and the ammonia and said solvent are removed from the treated mass by evaporation.

8. The process of claim 1 in which about to 50 pan-Its by weight or NH; in concentrated aqueous Jolution are used for each 1000 parts of vegetable meal and vitamin-containing oil in the mixture, and the ammonia and said solvent are removed from the treated mass by air-drying.

9. The process of claim 1 in which the vitamin-containing 011 comprises from 10 to 40% o! the total weight of vegetable meal and vitamincentaining oil.

10. The process of claim 1 in which the vegetable meal comprises wheat germ meal.

11. The process of claim 1 in which the vegetable mean comprises linseed oil meal.

t1,2. The process of claim 1 in which the vegeta le meal comprises flaxseed meal.

13. A composition of matter which comprises a fat-solvent and ammonia-treated, oil-bearing, vitamin-iortified, edible vegetable meal containing a substantial quantity of an added fat-soluble vitamin-containing oil, the total content 01 ole- 12 I individual particles or the meal being substantially nonunctuous, whereby the meal is or substantially tree-flowing character and resistant to loss of vitamin content.

15.-A composition of matter which comprises a vitamin-fortified, edible vegetable meal containing 5 to 40% by weight of an added fat-soluble, vitamin-containing oil, the total content of oleaginous matter amounting to to 50% of the weight of the meal, and the exterior surfaces of individual particles of the meal being substantially nonunctuous, whereby the meal is of substantially tree-flowing character and resistant to loss of vitamin content.

16. A composition of matter which comprises an acetone-ammonia-treated, vitamin-fortified, edible vegetable meal containing 10 to 40% by weight of a fat-soluble vitamin oil of external origin, having substantially the entire content of oleaginous matter distributed in the interior of individual particles of the meal, said entire content of oleaginous matter being not over 50% or the weight of the meal, and the exterior surface of individual particles of meal being substantially' nonunctuous, whereby the meal is sub? stantially free-flowing and resistant to loss of vitamin content.

17, The composition of matter of claim 14 in which the vegetable meal comprises wheat germ aginous matter being less than 50% of the weight of the meal, and the exterior surfaces of individual particles of the meal being substantially nonunctuous, whereby the meal is of substantially free-flowing character and resistant to loss of vitamin c'ontent.

14. A composition oi matter which comprises a fat-solvent and ammonia-treated, oil-bearing, vitamin-fortified, edible vegetable meal containing from 5 to 40% by weight 01 an added fatsoluble vitamin-containing oil, the total content of oleaginous matter being less than 50% of the weight of the meal, and the exterior surfaces of meal.

18. The composition of matter or claim 14 in which the vegetable meal compriseslinseed oil meal.

19. The composition of matter of claim 14 in which the vegetable meal comprises flaxseed meal.

20. A composition of matter prepared by the method set forth in claim 1.

LORAN O. BUXTON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

